US4224190A - Catalyst for dehydrogenating organic compounds, in particular amines, thiols, and alcohols, and a process for its preparation - Google Patents

Catalyst for dehydrogenating organic compounds, in particular amines, thiols, and alcohols, and a process for its preparation Download PDF

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US4224190A
US4224190A US05/925,930 US92593078A US4224190A US 4224190 A US4224190 A US 4224190A US 92593078 A US92593078 A US 92593078A US 4224190 A US4224190 A US 4224190A
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catalyst
carrier
sup
droplets
metal
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John Villadsen
Hans Livbjerg
Carl E. Moller
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation

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  • the present invention relates to a catalyst for dehydrogenating organic compounds, in particular amines, thiols, and alcohols.
  • the typical heterogeneous catalysts are characterized by the active material, e.g. a metal, being finely dispersed as crystallites in the porous, inactive carrier material, and by the active spots of the active material being susceptible to poisoning, e.g. due to the deposit of cracking products on the spots.
  • the active material e.g. a metal
  • the catalyst according to the invention is characterized by comprising a porous carrier containing liquid indium and/or zinc as an active catalytic material at the working temperature of the catalyst, said catalytic material in the shape of drops substantially with a diameter of 0.3-2 ⁇ being dispersed and maintained in the pore structure of the carrier.
  • An embodiment of the described catalyst wherein the liquid metal is indium is characterized by the catalyst having a porosity of 0.2-0.7 cm 3 /cm 3 , a BET-surface area of 0.5-10 m 2 /g, and an In-content of 0.05 to 10 g per 100 g of fired catalyst, preferably an In-content of 0.5-1.5 g per 100 g of fired catalyst.
  • the invention furthermore relates to a process for preparing the described catalyst, said process being characterized by mixing powdered In 2 O 3 and/or ZnO with an earth alkali metaloxide or hydroxide, preferably MgO or Mg(OH) 2 , whereafter the resulting mixture or substance is fired for 5 to 20 hours at a temperature of 900°-1150° C. and subsequently activated by introduction of a reducing gas, e.g. the organic compound in question in the form of vapor at 320°-440° C., until 2 to 3 times the calculated stoichiometric amount of gas for complete reduction of In 2 0 3 to In and/or ZnO to Zn has passed through the catalyst.
  • a reducing gas e.g. the organic compound in question in the form of vapor at 320°-440° C.
  • the contact angle metal carrier is more than 90°.
  • the contact angle In-MgO is for instance 133° at the melting point (156° C.) of indium. Therefore, the metal usually sweats out or runs out of the carrier unless if is retained by means of great external pressure.
  • the process according to the invention solves this problem since the reduction of In 2 O 3 -particles and/or ZnO-particles which were embedded in the carrier material during the mixing results in a final carrier material structure, wherein In-drops and/or Zn-drops formed from In 2 O 3 -particles and/or ZnO-particles during volume contraction, are present in cavities mutually connected through the pores of the carrier.
  • the pores permit free passage of the gas to the surfaces of the microscopic metal drops, a spontaneous gatherings or penetration of the metal, however, being impossible due to the difference in the size of the cavities and the pore diameter.
  • FIG. 1 of the drawing illustrates a fractured surface in a catalyst pill according to the invention, drawn from a scanning electron microscope photograph.
  • FIG. 1 clearly shows how spherical metal droplets 1 of from 0.5 to 2.5 ⁇ in size are separated by a duct system 2 of far less diameter than the pores encasing the droplets 1.
  • U.S. Pat. No. 3,542,878 discloses a catalyst prepared by impregnating a porous carrier with an aqueous solution of a tin compound and subsequently drying the same or by precipitating Sn(OH)Cl, xH 2 O on the carrier, whereby the tin compound is reduced with hydrogen. At about 250° C. and a reaction pressure of 75 ata, this catalyst results in aldol condensation of carbonyl compounds, and the catalytic activity is imputed to fused, metallic tin.
  • the process of the invention provides a stable catalyst material, wherein a metal (indium and/or zinc) is dispersed.
  • a metal indium and/or zinc
  • the catalyst of the invention is quite different from the catalysts presently used within the industry for a number of dehydrogenation reactions, and by virtue of its high activity and selectivity it provides, as compared to known catalysts, a possibility of substantially increasing the reaction rate per unit of reactor volume and the product quality.
  • the use of the catalyst for dehydrogenating alcohols is described, and in particular the use of a catalyst based on indium for dehydrogenating 2-butanol is mentioned, but catalysts based on zinc are also described, the preparation of such being described in the following Example 10.
  • Zinc is considerably less expensive than indium and would therefore be preferred to indium, if there were not at the same time some drawbacks that make zinc technically less suitable than indium.
  • the catalytic effect of catalysts based on zinc has been proved, however.
  • 2-butanon is an industrially important solvent, and 85% of the world market consumption is prepared by dehydrogenating 2-butanol.
  • the used catalysts can be mentioned: copper-brass-chips or (rusty) iron filings, either alone or coated with a layer of one or more metaloxides such as ZnO, MgO, Na 2 O, Ce 2 O 3 , Cr 2 O 3 , ZrO 2 , ThO 2 and Bi 2 O 3 .
  • metaloxides such as ZnO, MgO, Na 2 O, Ce 2 O 3 , Cr 2 O 3 , ZrO 2 , ThO 2 and Bi 2 O 3 .
  • the activity of the catalyst is, of course, of great importance since it determines the amount of reactant, which is convertible per unit of time by means of a predetermined amount of catalytic material, but the selectivity of the catalyst is of even greater importance.
  • the selectivity can be expressed as the portion of reactant used for the conversion, which is converted into the desired product.
  • the carrier for the liquid catalytic metal several circumstances are to be considered.
  • the fired carrier material In the first place the fired carrier material must have a large pore volume and an appropriately small or narrow pore width in order to maintain the fused metal, and so that a large contact area between the reactant and the catalyst and easy passage of the reactant into the interior of the carrier are ensured. Subsequently, the carrier may not to any appreciable extent catalyze undesired side reactions.
  • Mg or Zn spinel (MgAl 2 O 4 or ZnAl 2 O 4 )
  • the basic and acidic properties of the carrier material can be neutralized and a carrier obtained, which in the respect of mechanical strength is somewhat better than a fired MgO-carrier, cf. the following Example 7.
  • the selectivity of the spinel carrier is not nearly as good as the selectivity of the MgO carrier, and a MgO-carrier is therefore preferred in order not to reduce the selectivity of the catalyst in general.
  • In 2 O 3 is mixed with MgO, whereby powdered In 2 O 3 is mixed with powdered MgO containing 1 to 5% lubricant, preferably Mg-stearate, and compressed, preferably into pills or pearls, before the firing is performed.
  • powdered In 2 O 3 is mixed with powdered MgO containing 1 to 5% lubricant, preferably Mg-stearate, and compressed, preferably into pills or pearls, before the firing is performed.
  • In 2 O 3 may be mixed with Mg(OH) 2 , whereby powdered In 2 O 3 is mixed with an aqueous Mg(OH) 2 -gel during grinding to form a paste containing In 2 O 3 -granules under 5 ⁇ in size uniformly dispersed in the Mg(OH) 2 vehicle, whereafter the paste is dried at 100°-150° C. for obtaining a dry matter content of 40-60% and extruded before the firing is performed.
  • a high firing temperature improves the mechanical strength of the carrier material, but simultaneously reduces its pore volume and interior surface.
  • the best result is obtained when a catalyst based on MgO is fired at a temperature of just under 1000° C. for 5 to 20 hours.
  • a MgOAl 2 O 3 -carrier having the stoichiometric relations between MgO and Al 2 O 3 necessary to form a spinel must be fired at more than 1300° C. to ensure formation of the spinel structure, cf.
  • Example 7 Firing the MgO-In 2 O 3 catalyst at 950° C. followed by a second firing at 1040° C.
  • the catalyst can be separately activated, whereby 5 to 10 times the stoichiometric amount H 2 is passed across the fired catalyst pills at 400° C. during the collecting of the yellow to yellowish gray volatile In 2 O and InO vapors condensed in the cold portion of the activating reactor.
  • test set-ups used and the analysis method for In are briefly described below to explain the runs mentioned in the Examples.
  • Examples 2 to 7 a recirculation reactor is used.
  • a constant feed flow of 2-butanol is passed by means of a dosage pump into an evaporator, wherein the 2-butanol is evaporated at 210° C.
  • nitrogen can be mixed in the butanol flow and thereby act as a neutral diluent material, but the runs described in the Examples have been carried out without this addition of inert gases.
  • the gas is passed into the reactor loop comprising the reactor and an outer recirculation loop.
  • a bellow pump yielding 28 l gas/min.
  • the measured conversion ratio ⁇ may be correlated with the kinetics of the reaction r through the following expressions for an ideally stirred tank reactor with pure reactant in the feed flow:
  • F may mean kilograms per hour
  • W may mean kilograms of catalyst
  • ⁇ is the conversion ratio ranging from 0 to 1.
  • the factor 1+ ⁇ in the denominator which is due to the volume increase at the reaction, is thus almost 2 when ⁇ ⁇ 1. This means that a proportionality is almost obtained between F ⁇ /W and (1- ⁇ ), provided the reaction temperature is selected in such a manner that the backward reaction is insignificant.
  • the reaction is more than 98% displaced towards the formation of ketone provided the temperature is above 325° C., and the backward reaction can therefore be disregarded.
  • the velocity constant of the first order is k (h -1 ) calculated as ##EQU3## and subsequently the capacity of an equivalent integral reactor for obtaining the recirculation reactor result is calculated as ##EQU4## for various values of ⁇ .
  • the measuring of the conversion ratio ⁇ is performed by means of gas phase chromatography, whereby a sample is automatically taken in a test loop every 20 minutes. Areas corresponding to ketone, alcohol and side products are automatically calculated and transferred to a punched paper tape, from where they can later be further examined and transferred into a final form as illustrated in the Tables 1 to 7, showing the calculation results for the activity (S and k) and the selectivity.
  • the entire set-up is carefully supervised so that the reactor temperature and flow velocities are regulated within narrow limits.
  • a programmed temperature cycle of 100° C. in steps of 15° C. may be run through during 24 hours in order to obtain acidity measurements as a function of the temperature.
  • the oxide When In is present in oxide form, the oxide is reduced with H 2 at 420° C. before boiling with acid.
  • the activity for the In-containing catalyst is many times larger than the activity for the carrier alone at all test temperatures.
  • Analytically pure MgO with 5% Mg-stearate as a binding agent is pelletized at 4 different pressures. Each sample is fired at two different temperatures, 950° C. and 1040° C. for 20 hours. The pellets have a diameter of 6 mm and a weight per mm height of the pills of 0.0436, 0.0410, 0.0347 and 0.0334 grams per mm respectively. The weight of the sample pelletized at the highest pressure is the greatest.
  • the weight loss is 17%, both when fired at 950° C. and at 1040° C.
  • the high weight loss is due to the fact that besides stearate, hydroscopically combined water also evaporates from MgO.
  • the pill diameter is insignificantly changed and amounts to 96-98% of the thickness measured before the firing.
  • a second MgO-sample comprising 5% Mg-stearate is pelletized and fired for 20 hours at 950° C.
  • the firing loss is 19.9%. Neither the pill diameter nor the pill thickness are changed during the firing.
  • the results of the activity (k) and the selectivity (S) are illustrated in Table 1.
  • In 2 O 3 was added to a carrier material with the same composition as the carrier material described in Examples 1 to 3 in an amount corresponding to a content of 3% In in the fired catalyst.
  • the sample was pelletized, and the pellets were weighed and measured, after which they were fired at 950° C. for 20 hours.
  • the weight loss was 20.2%, i.e. almost corresponding to the weight loss in the Examples 1 and 2.
  • the pellet height was, however, reduced from 2.95 mm to 2.73 mm, whereas the pellet diameter was reduced from 6 mm to 5.6 mm, i.e. considerable shrinking occurred.
  • Pellets containing from 0.1% to 7.3% In were prepared as in Example 4 and used as a catalyst in the recirculation reactor.
  • a partial sample was removed from the sample containing 0.1% In (Run 62 in Table 2). After firing at 950° C. for 20 hours this partial sample was subjected to a second firing at 1040° C. for an additional 20 hours.
  • the activity of this sample (Run 62a) is compared in Table 2a to the sample fired only once at 950° C. The second firing at the higher temperature causes a certain drop in activity (vitrification) and a very slowly increasing selectivity from 98.9% at all three temperatures during Run 62, to 99.0% during Run 62a.
  • the hardness and the strength of said catalyst are obviously a function of the In-content.
  • a pure MgO carrier fired at 950° C. can be crumbled manually, whereas a sample containing only 1% In 2 O 3 is durable, also when subjected to slight impacts and blows.
  • the shrinking and the increase in hardness are ascribed to a partial formation of MgIn 2 O 4 .
  • a quartz glass carrier having an almost uniform pore width of 306.0 nm was impregnated with an In(NO 3 ) 3 -solution.
  • the sample was initially dried at 80° C. for 4 hours and subsequently at 180° C. for an additional 4 hours.
  • a sample of 5.3 grams contained 17% In.
  • FIG. 2 A microscopical examination of the glass particles (FIG. 2) showed that In had collected in large drops on the surface of the carrier. Some of the drops had fallen off and were present within the reactor.
  • the above gelation procedure was repeated with Zn powder instead of ZnO powder.
  • the catalyst pellets were colored grayish black after 2 hours as a consequence of the carbon deposit on the SiO 2 -carrier.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US05/925,930 1977-07-22 1978-07-19 Catalyst for dehydrogenating organic compounds, in particular amines, thiols, and alcohols, and a process for its preparation Expired - Lifetime US4224190A (en)

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DK3315/77 1977-07-22
DK331577A DK153293C (da) 1977-07-22 1977-07-22 Katalysator til dehydrogenering af organiske forbindelser, isaer aminer, thioler og alkoholer, og fremgangsmaade til fremstilling deraf

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US (1) US4224190A (enrdf_load_stackoverflow)
JP (1) JPS5452694A (enrdf_load_stackoverflow)
BR (1) BR7804735A (enrdf_load_stackoverflow)
CA (1) CA1118746A (enrdf_load_stackoverflow)
DE (1) DE2831465A1 (enrdf_load_stackoverflow)
DK (1) DK153293C (enrdf_load_stackoverflow)
FI (1) FI66127C (enrdf_load_stackoverflow)
FR (1) FR2397877A1 (enrdf_load_stackoverflow)
GB (1) GB2002253B (enrdf_load_stackoverflow)
IT (1) IT1099012B (enrdf_load_stackoverflow)
NL (1) NL7807849A (enrdf_load_stackoverflow)
SE (1) SE438104B (enrdf_load_stackoverflow)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5597894A (en) * 1995-06-05 1997-01-28 The Louisiana State University Medical Center Foundation Multi-tyrosinated somatostatin analogs
US5968903A (en) * 1998-05-07 1999-10-19 Biomeasure, Incorporated Inhibition of H. pylori proliferation
US6573413B2 (en) 2000-04-19 2003-06-03 Solutia Inc. Process for activating catalyst for the hydroxylation of aromatics
US20070003476A1 (en) * 2003-11-26 2007-01-04 Asemblon, Inc. Method and device for hydrogen storage and delivery
US20090042721A1 (en) * 2007-08-09 2009-02-12 Nissan Motor Co., Ltd Inorganic fiber catalyst, production method thereof and catalyst structure
CN108855153A (zh) * 2018-05-28 2018-11-23 河南师范大学 一种淡黄色碱式氯化亚锡可见光响应光催化材料的制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0130068B1 (en) * 1983-06-23 1988-03-23 Sumitomo Chemical Company, Limited A process for producing formaldehyde
JP6541073B2 (ja) * 2016-03-07 2019-07-10 Ｊｘｔｇエネルギー株式会社 低級炭化水素用の脱水素触媒、及び芳香族化合物の製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3254055A (en) * 1962-10-18 1966-05-31 Eastman Kodak Co Gallium catalyst combinations for linear polyester making
US3338972A (en) * 1965-01-08 1967-08-29 Eastman Kodak Co Dehydrogenation of 2-norcamphanol
US3523964A (en) * 1967-04-10 1970-08-11 Olin Corp Preparation of aromatic isocyanates

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1028167A (en) * 1964-03-06 1966-05-04 British Petroleum Co Improvements in or relating to catalysts
FR1543933A (fr) * 1966-11-28 1968-10-31 Inst Francais Du Petrole Procédé et catalyseur de fabrication de cétones cycliques, par déshydrogénationcatalytique d'alcools cycliques
US3824178A (en) * 1973-04-27 1974-07-16 Shell Oil Co Hydrocracking petroleum and related materials

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3254055A (en) * 1962-10-18 1966-05-31 Eastman Kodak Co Gallium catalyst combinations for linear polyester making
US3338972A (en) * 1965-01-08 1967-08-29 Eastman Kodak Co Dehydrogenation of 2-norcamphanol
US3523964A (en) * 1967-04-10 1970-08-11 Olin Corp Preparation of aromatic isocyanates

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5597894A (en) * 1995-06-05 1997-01-28 The Louisiana State University Medical Center Foundation Multi-tyrosinated somatostatin analogs
US5968903A (en) * 1998-05-07 1999-10-19 Biomeasure, Incorporated Inhibition of H. pylori proliferation
US6573413B2 (en) 2000-04-19 2003-06-03 Solutia Inc. Process for activating catalyst for the hydroxylation of aromatics
US20070003476A1 (en) * 2003-11-26 2007-01-04 Asemblon, Inc. Method and device for hydrogen storage and delivery
US8459032B2 (en) 2003-11-26 2013-06-11 Asemblon, Inc. Method and device for hydrogen storage and delivery
US20090042721A1 (en) * 2007-08-09 2009-02-12 Nissan Motor Co., Ltd Inorganic fiber catalyst, production method thereof and catalyst structure
US7910514B2 (en) * 2007-08-09 2011-03-22 Nissan Motor Co., Ltd. Inorganic fiber catalyst, production method thereof and catalyst structure
CN108855153A (zh) * 2018-05-28 2018-11-23 河南师范大学 一种淡黄色碱式氯化亚锡可见光响应光催化材料的制备方法
CN108855153B (zh) * 2018-05-28 2021-03-16 河南师范大学 一种淡黄色碱式氯化亚锡可见光响应光催化材料的制备方法

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FI66127B (fi) 1984-05-31
GB2002253A (en) 1979-02-21
FI782306A7 (fi) 1979-01-23
NL7807849A (nl) 1979-01-24
DK153293B (da) 1988-07-04
GB2002253B (en) 1982-03-24
IT1099012B (it) 1985-09-18
SE7807793L (sv) 1979-01-23
BR7804735A (pt) 1979-04-10
FI66127C (fi) 1984-09-10
DK153293C (da) 1988-11-14
SE438104B (sv) 1985-04-01
DE2831465A1 (de) 1979-02-01
FR2397877A1 (fr) 1979-02-16
DK331577A (da) 1979-01-23
JPS6211616B2 (enrdf_load_stackoverflow) 1987-03-13
DE2831465C2 (enrdf_load_stackoverflow) 1992-03-19
IT7825971A0 (it) 1978-07-21
CA1118746A (en) 1982-02-23
JPS5452694A (en) 1979-04-25

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